Polyetherquinoxalines

ABSTRACT

Polyetherquinoxalines are provided which are useful as injection molding compounds. The polyetherquinoxalines are the product of reaction of organic tetramine and bis(aromatic ether aromatic diketones).

United States Patent 1191 Heath et al.

14 1 Dec. 3, 1974 POLYETHERQUINOXALINESI Inventors: Darrell R. Heath, Overland Park,

Kans; Joseph G. Wirth, Schenectady, NY.

Assignee: General Electric Company,

Schenectady, NY.

Filed: Nov. 23, 1973 App]. No.: 418,250

us. c1 260/50, 161/257, 260/326 N, 260/33.4 P, 260/338 R, 260/37 N, 260/49,

1111. c1 C08g 33/02 Field 61 Search 260/47 R, 49, 50,65

References Cited UNITED STATES PATENTS Stillc 260/50 Primary ExaminerLester L. Lee Attorney, Agent, or Firm-William A. Teoli; Joseph T. Cohen; Jerome C. Squillaro 8 Claims, N0 Drawings l POLYETHERQUINOXALINES The present invention relates to polyetherquinoxalines which are made by effecting reaction between organic tetramines and bis(aromatic ether aromatic diketones).

As shown in US. Pat. No. 3,730,946 of Heath et al., assigned to the same assignee as the present invention, certain dinitro benzenoid compounds can be employed with alkali metal bisphenolates to make a variety of I novel polymers. It has now been discovered that nitrodisplacement of diketones of formula,

with alkali metal salts of dihydric phenols of the formula,

MOROM, also can'be employed to provide bis(aromatic ether omatic diketones) of the formula,

where R is a monovalent radical selected from hydrogen and a C hydrocarbon and R is a divalent aromatic radical having from 6-30 carbon atoms.

Radicals included by R are, for example, C alkyl such as methyl, ethyl propyl, butyl, pentyl, etc. aryl, such as phenyl, tolyl, xylyl, naphthyl, etc. Radicals included by Rai e, for example, (a) the following divaand (b) divalent organic radicals of the general formula where X is a member selected from the class consisting of divalent radicals of the formulas, C,,H

-O, and -.S, where m is 0 or I, and y is a whole number from I to 5.

The bis(aromatic ether aromatic diketones) of formula l, hereinafter referred to as the tetra ketones" can be employed as plasticizers in a variety of organic resins such as polyvinylchloride, polyimides, polyurethanes, etc. In addition, the tetra ketones of the present invention can be reacted with tetramines of the formula,

' is Hi Nit;

11 Nfiz NHE where R is a tetravalent C aromatic organic radical defined below, to form polyetherquinoxalines having injection molding characteristics, consisting essentially of the following chemically combined units L a g ii r where R and R are as previously defined.

Unlike the polyquinoxalines shown by Aug! et al;, US. Pat. No. 3,654,226 and Stille, US. Pat. No. 3,661,850, the polyetherquinoxalines of the present invention have chemically combined aromatic ether linkages --ORO-, which render such materials injection moldable and soluble in relatively low polarity organic solvents such as chloroform and methylene chloride as well as the more polar solvents such as dimethylformamide, dimethylacetamide, etc. I There is provided by the present invention, moldable polymeric materials having recurring quinoxaline groups and an intrinsic viscosity'in the'range of from 0.1 to 2.0 which is the product of reaction of a tetra where X is a member selected from the class consisting of C,,H O,

and

ple,

and S--, where m is or l, and y is a whole number from. 1 to 5.

lncluded by the tetra carbonyl compounds of formula l are, for example,

l, l -bis(4-hydroxyphenyl )propane; 2,2-bis( 4hydroxyphenyl )pentane; 3,3 -bis( 4-hydroxyphenyl )pentane; 4,4'-dihydroxybiphenyl;

included by the tetramine of formula ll are, for exam- InN- Nm lIzN- N H2 etc. Additional tetramines are shown in Stille, US. Pat. No. 3,661,850. 7

The alkali metal salts of the dihydric phenols which can be used to make the tetracarbonyl compounds of formula (I) by nitro-displacement are well known and include, for example, the disodium salt of 4,4- dihydroxybiphenyl, the disodium salt of 4,4- dihydroxydiphenyl sulfone, the dipotassium salt of 4,4'dihydroxydiphenyl sulfide, etc. These alkali metal diphenoxides can be made by effecting reaction between an alkali metal hydroxide and a dihydric phenol. For example, the alkali metal salt of bisphenol-A can be obtained by reacting 2 moles of sodium hydroxide per mole of bisphenol-A. Again, alkali metal diphenoxides also can be made by adding 0.58 part of fresh cut of sodium metal to 75 parts of anhydrous methanol, with a magnetic stirrer under a nitrogen atmosphere.

I There is added to the mixture at the termination of the sodium reaction, 2.875 parts of bisphenol-A followed by evaporating the resulting solution to dryness. There is obtained a white solid upon drying the mixture further at 70C.

Dihydric phenols which can be used to make the alkali metal salts of the dihydric phenols are, for example,

2,2-bis( 2-hydroxyphenyl)propane;

2,4-dihydroxydiphenylmethane;

bis (2-hydroxyphenyl)methane;

2,2-bis(4-hydroxyphenyl)propane, hereinafter identified as bisphenol-A or BPA;

1 1 -bis( 4-hydroxyphenyl)ethane;

4,4'-dihydroxy-3,3',5,5'-tetramethylbiphenyl; 2,4'dihydroxybenzophenone; 4,4'-dihydroxydiphenyl sulfone; 2,4'-dihydroxydiphenyl sulfone; 4,4'dihydroxydiphenyl sulfoxide; 4,4-dihydroxydiphenyl sulfide;

hydroquinone;

resorcinol;

3,4'-dihydroxydiphenylmethane;

4,4'-dihydroxybenzophenone;

and 4,4-dihydroxydiphenyl ether.

in the practice of the invention, the tetramine and tetra carbonyl compound is contacted under a nitrogen atmosphere in the presence of a cresol solvent. The mixture is then poured into a precipitating solvent to recover polymeric product.

Optimum results are achieved when substantially equal moles of the tetramine and tetra carbonyl compound are employed, although there can be used from 0.8 to 1.2 moles of tetramine per mole of tetra carbonyl compound. Temperature of from 25 to 200C can be employed with agitation of the reactants.

Cresol solvent which can be used can be o-, p-, or mcresol, or a mixture thereof known as cresylic acid, as well as a mixture of such cresols and phenols. Reaction time can vary considerably and will depend upon such factors as degree of agitation, temperature, nature and proportion of reactants, etc. Accordingly from 0.5 to 20 hours willnot'be unusual. The crude polymeric product can be recovered by pouring the reaction mixture into an excess of precipitating solvent such as methanol, etc. The final polyetherquinoxaline can be reprecipitated by standard techniquesuch as redissolving in chloroform andprecipitating from methanol.

The polyetherquinoxalines of the present invention y can be employed with carbon fibers to make composites reinforced with finely divided fillers such as silica gloss fibers, etc. in a proportion of from 50 to 200 parts of filler per parts. of polymer. The resulting reinforced polymers are injection moldable.

ln orderthat those skilled in the art will be better able to practice the invention, the following examples are given by way of illustration and not by way of limitation. All parts are by weight.

EXAMPLE 1 ring to 2,400 parts of 1N hydrochloric acid and 900 EXAMPLE 2 parts of chloroform. After one hour of stirring the layers were separated. The chloroform solution was extracted with six 300 part portions of 1N hydrochloric The procedure of Example 1 was repeated except in place of 3,3',4,4-tetraminobiphenyl there was employed 3,3,4,4'-tetraminobenzophenone. There was dried wlth magneslum Sulfate and smpped of 5 obtained 3.6] parts representing a 96 percent yield of Vent under reduced P Q- There was Obtained a polymeric reaction product having an intrinsic viscos- Parts of a crude Product which was recFystamzed from ity in chloroform at 25C. of 0.37. Based on method of 1,000 Parts Of acetic acid- There was Obtained preparation and elemental analysis, the product was a Parts of a Product having a melting P 0f polyetherquinoxaline consisting essentially of the foll66168C. Based on method of preparation, H- lowing chemically combined units,

NMR spectrum, C-NMR spectrum, mass spectrum, EXAMP 3 and elemental analysis, the product was a tetra car- The procedure of Example 1 was repeated except bonyl having e formula that in place of 3,3,4,4'-tetraminobiphenyl, there was Another recrystallization of benzene/cyclohexane reemployed 3,3',4,4'-tetrarninodiphenyl ether. There sulted in a melting point of l67l69C. was obtained 3.86 parts whichrepresented a 97 per- There was added 2.8733 parts of the above tetracarcent yield of a polymeric reaction product having an bony] compound along with 5 parts of cresol to a solu- 0 intrinsic viscosity in chloroform of 1.02. Based on tion of 1.0216 parts of 3,3,4'-tetraminobiphenyl in 20 method of preparation, C-NMR spectrum and eleparts of cresol. The resulting mixture was stirred for 2.2 mental analysis, the product was a polyetherquinoxahours at' a temperature of 9598C. The mixture beline consisting essentially of the following chemically came homogeneous after a few minutes of heating combined units,

while the viscosity gradually increased. The mixture EXAMPLE 4 was then refluxed for 15 minutes, cooled and added slowly to a large excess of methanol in a blender. There A polyetherquinoxaline was prepared in accordance was obtained 3.51 parts of a precipitate which was diswith the procedure of Example 1, using 3,3',4,4- ol n parts of chloroform and reprecipitated tetraminodiphenyl sulfone in place of the tetramine of from methanol. There was obtained 3.01 parts of prod- Example 1. There was obtained 3.48 parts which repreuct representing a yield of percent, which had an insented a 9l percent yield of a polymeric reaction prodtrinsic viscosity of 1.01 in chloroform. Based on 50 uct having an intrinsic viscosity of 0.19. Based on method of preparation and elemental analysis the prodmethod of preparation and elemental analysis the product was a polyetherquinoxaline consisting essentially of uct was a polyetherquinoxaline consisting essentially of the following chemically combined units, the following chemically combined units, L, N

N I N 7 r 8 EXAMPLE 2. A moldable polymeric material in accordance with A tetra carbonyl compound was prepared in accorclam where R115 dance with the procedure of Example 1, except that 2,2-bis-(4-hydroxyphenyl) methane was employed in Y O place of 4,4-dihydroxybiphenyl. There was obtained a 5 70 percent yield of product. Based on method of preparation, elemental analysis, 1-! NMR, C NMR and mass 3. A moldable polymeric material in accordance with spectra, the product was claim 1, where R is In accordance with the procedure of Example 1,

equal moles of the above-described tetra carbonyl I compound and tetraminobiphenyl ether was reacted in :3@ cresol. There was obtained a 74 percent yield of a on,

polyetherquinoxaline. The polymer had an intrinsic viscosity in cresol of 0.17. Based on method of preparation and its C NMR spectrum, the polymer consisted 4. A moldable polymeric material in accordance with essentially of the following chemically combined units, claim 1, where R is J I (EH3 n A hundred parts of the above p olyetherquinoxaline is blended with 50 parts of fume silica. The blend, is molded at 250C for 5 minutes under a pressure of 4,000 psi. A tough thermoplastic pellet is obtained;

Although the above examples are limited to only a few of the very-many polyertherquinoxalines which can 5. A moldable polymeric mater al in accordance with I be made in accordance with the present invention, it Clam where R is should be understood that the present invention is di- O rected to a much broader class of polyetherquinoxag lines which can be made by effecting reaction between 40 substantially equal moles of the tetra carbonyl coml 1 pound of formula I and the. tetramine of formula ll. 5

What we claim as new and desire to secure by Letters A moldable Polymeric material in accordance Patent of the United States is: I claim 1, when? R2 is l. Moldable polymeric materials having recurring quinoxaline groups and an intrinsic viscosity of from I l l 0.1 to 2.0 in chloroform at 25C consisting essentially '@o- O of the following chemically combined units I 7. A moldable polymeric material in accordance with I claim 1, where R is N N i I 3% \Rg T I l- I 8. A polyetherquinoxaline having an intrinsic viscoswh r R i a di l aromatic i l having f ity of from 0.1 to 2.0 in chloroform at 25C and consist- 6-30 carbon atoms, and R is a tetravalent aromatic orlng essentially of Chemically combined units of the .ganic radical. I y Y mula 

1. MOLDABLE POLYMERIC MATERIALS HAVING RECURRING QUINOXALINE GROUPS AND AN INTRINSIC VISCOSITY OF FROM 0.1 TO 2.0 IN CHLOROFORM AT 25*C CONSISTING ESSENTIALLY OF THE FOLLOWING CHEMICALLY COMBINED UNITS
 2. A moldable polymeric material in accordance with claim 1, where R1is
 3. A moldable polymeric material in accordance with claim 1, where R1 is
 4. A moldable polymeric material in accordance with claim 1, where R2 is
 5. A moldable polymeric material in accordance with claim 1, where R2 is
 6. A moldable polymeric material in accordance with claim 1, where R2 is
 7. A moldable polymeric material in accordance with claim 1, where R2 is
 8. A polyetherquinoxaline having an intrinsic viscosity of from 0.1 to 2.0 in chloroform at 25* C and consisting essentially of chemically combined units of the formula 